Zimmermann René R, Hahn Tobias, Reschetilowski Wladimir, Armbrüster Marc
Materials for Innovative Energy Concepts, Faculty of Natural Sciences, Institute of Chemistry, University of Technology Chemnitz, Straße der Nationen 62, 09107, Chemnitz, Germany.
Leibniz Institute for Catalysis at the University of Rostock (LIKAT Rostock), Albert-Einstein-Str. 29a, 18059, Rostock, Germany.
Chemphyschem. 2017 Sep 20;18(18):2517-2525. doi: 10.1002/cphc.201700535. Epub 2017 Aug 16.
Intermetallic GaPd is a highly selective and stable catalyst for the semi-hydrogenation of acetylene. Knowledge of the underlying reaction kinetics is essential to gain a deeper understanding of the selective hydrogenation on this catalytic material. To date, there has been no experimental kinetic data published for this reaction on a well-defined intermetallic catalyst possessing isolated active sites. Kinetic measurements are performed at 140-200 °C, revealing an apparent activation energy of 29(2) kJ mol . GaPd is shown to be the first binary catalyst material, which shows a positive reaction order (0.89) with respect to acetylene at 200 °C. The influences on the extent of acetylene conversion, specific activity and selectivity to ethylene, ethane, and higher hydrocarbons are determined by a 2 factorial experiment following a design of experiments approach. Temperature and pressure have the strongest impact on these values. The results allow optimal operation for achieving high ethylene yields. A comparison of the reaction kinetics on GaPd with experimental results obtained for GaPd reveals different orders of reaction of H and C H on the two compounds.
金属间化合物GaPd是乙炔半加氢反应的高选择性和稳定催化剂。了解其潜在的反应动力学对于深入理解该催化材料上的选择性加氢反应至关重要。迄今为止,尚未有关于在具有孤立活性位点的明确金属间催化剂上该反应的实验动力学数据发表。动力学测量在140 - 200°C下进行,显示出表观活化能为29(2) kJ mol 。GaPd被证明是第一种二元催化剂材料,在200°C时对乙炔呈现正反应级数(0.89)。采用实验设计方法通过二因素实验确定了对乙炔转化率、比活性以及对乙烯、乙烷和高级烃的选择性的影响。温度和压力对这些值的影响最大。这些结果有助于实现高乙烯产率的最佳操作。将GaPd上的反应动力学与GaPd的实验结果进行比较,发现两种化合物上H₂和C₂H₂的反应级数不同。